JP3204514B2 - Carbonylation catalyst system - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel catalyst system containing a tertiary amine and to the carbonylation of acetylenically unsaturated compounds and olefinically unsaturated compounds (Car
b.

[0002]

BACKGROUND OF THE INVENTION Many methods are known in the art for carbonylating acetylenically unsaturated compounds and olefinically unsaturated compounds. An overview of such methods is given by J. Falbe, "New Synthesis with Carbon Monoxide (New Synthese).
s with Carbon Monoxide) ”,
Springer-Ve
rlag), Berlin Heidelberg New York,
1980, pages 273-291. Typically, these methods involve the conversion of acetylenically unsaturated compounds or olefinically unsaturated compounds to carbon monoxide and optionally a nucleophile having a removable hydrogen atom in the presence of a carbonylation catalyst system. Reacting with the compound. In many cases, the carbonylation catalyst system includes a Group VIII metal source and a ligand such as phosphine. More recently, several processes for the carbonylation of acetylenically unsaturated and olefinically unsaturated compounds have been disclosed which involve the use of a carbonylation catalyst system consisting of a Group VIII metal compound, especially a palladium compound, phosphine and a protic acid. These methods proceed at significantly higher reaction rates.

[0003] European Patent Application Publication EP-A1-106
No. 379, EP-A1-235864, EP-A1-
No. 274,795 and EP-A1-279,777 disclose a process for the carbonylation of olefinically unsaturated compounds in which a catalyst system comprising a palladium compound, a triarylphosphine and a protonic acid is used. In all of these examples, the triarylphosphine used is triphenylphosphine. European Patent Application Publication EP-
A1-0186228 discloses a method for the carbonylation of acetylenically unsaturated compounds using a catalyst system consisting of a palladium compound, phosphine and a protonic acid. The example illustrates the use of an optionally substituted hydrocarbylphosphine, such as triphenylphosphine. More recently, several methods for carbonylating acetylenically unsaturated compounds and olefinically unsaturated compounds have been described, including the use of catalyst systems consisting of palladium compounds, pyridylphosphines and acids.

[0004] European Patent Application Publication EP-A1-259
No. 914, EP-A1-282142 and EP-A
No. 1-305012 uses a catalyst system comprising a palladium compound, pyridylphosphine and a protonic acid,
A method for the carbonylation of olefinically unsaturated compounds is disclosed. European Patent Application Publication No. EP-A1-0271
No. 144 discloses a method for carbonylating an acetylenically unsaturated compound using a catalyst system comprising a palladium compound, pyridylphosphine and a protonic acid.
Not only do the above-mentioned European patents disclose catalysts additionally containing tertiary amines, but also such catalyst systems are of interest in the carbonylation of acetylenically unsaturated and olefinically unsaturated compounds. It does not even suggest that it causes it. Since tertiary amines are basic compounds, they were expected to have a significant inhibitory effect on the performance of the acid-containing catalyst system. In fact, Applicants have found that the inclusion of a tertiary amine in a triarylphosphine-based catalyst system significantly impairs the performance of the catalyst system in olefin carbonylation.

[0005] Surprisingly, however, the Applicant has found that using a catalyst system comprising a palladium compound, pyridylphosphine, a protonic acid and a tertiary amine, the acetylenically unsaturated compounds and the olefinically unsaturated compounds can be improved. It has now been found that the carbonylation can be carried out at different reaction rates.

[0006]

DETAILED DESCRIPTION OF THE INVENTION Accordingly, the present invention comprises: a) a source of a Group VIII metal; b) a phosphine having an aromatic substituent containing an imino nitrogen atom; c) a protic acid; and d) a tertiary amine. A catalyst system is provided.

The catalyst system of the present invention has been found to exhibit high activity in the carbonylation of acetylenically unsaturated compounds and olefinically unsaturated compounds. This finding indicates that it is highly active Group VIII metal / pyridylphosphine /
It was very surprising since it means that the protonic acid catalyst system can be used under basic conditions to carbonylate acetylenically unsaturated and olefinically unsaturated compounds. Many reactions, which can only be performed satisfactorily under basic conditions, are now possible. For example, it has been found that esters of acid-sensitive hydroxyl compounds such as silanols and tertiary alcohols can be produced using the catalysts of the present invention with satisfactory selectivity.

Surprisingly, it has also been discovered that the catalyst system of the present invention exhibits improved tolerance to allene, a common impurity of acetylenically unsaturated compounds.
Still further, it has surprisingly been found that alkoxymethoxyalkanoates can be prepared by carbonylating alkenes with alkanols and formaldehyde in the presence of the catalyst system of the present invention.
Still further, it has also been surprisingly discovered that the catalyst systems of the present invention are more stable over a longer period of time than the corresponding catalyst systems without tertiary amines. The catalyst system of the present invention includes a Group VIII metal source. The Group VIII metal source can be a metallic element or, preferably, a compound of a Group VIII metal.

Examples of Group VIII metals are iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum. The catalyst system of the present invention preferably includes a source of a palladium compound. Examples of Group VIII metal compounds are salts, for example nitrates; sulfates; sulfonates; phosphonates; perhalates; alkanic carboxylic acids having up to 12 carbon atoms, for example salts of carboxylic acids such as acetic acid;
And salts of hydrohalic acids. Hydrohalic acid salts are not preferred because halogen ions tend to be corrosive. Other examples of Group VIII metal compounds include complexes, such as complexes with acetylacetonate, phosphine and / or carbon monoxide.
For example, compounds of the Group VIII metal include palladium acetylacetonate, tetrakis-triphenylphosphine palladium, bis-tri-o-tolylphosphine palladium acetate, bis-diphenyl-2-pyridylphosphine palladium acetate, and tetrakis-diphenyl-2-pyridylphosphine palladium. , Bis-di-o-tolylpyridylphosphine palladium acetate, or bis-diphenylpyridylphosphine palladium sulfate.

[0010] The catalyst system used in the process of the present invention further comprises a phosphine having an aromatic substituent containing an imino nitrogen atom. The term "imino nitrogen atom" as used herein refers to a compound of the formula

Embedded image Means a nitrogen atom that can be represented by the structural formula of an aromatic substituent containing nitrogen. For example, when the aromatic substituent is a pyridyl group, the structural formula of the aromatic substituent is

Embedded image Becomes

The phosphines preferably contain one or two phosphorus atoms. Each phosphorus atom has three substituents. At least one of these substituents is an aromatic substituent containing an imino nitrogen atom. The remaining substituents are
Preferably, it is selected from optionally substituted aliphatic and aromatic hydrocarbyl groups. When the phosphine contains more than one phosphorus atom, for example

Embedded image And more than one phosphorus atom can be assigned to one substituent.

The aromatic substituent containing an imino nitrogen is preferably a six-membered ring containing one, two or three nitrogen atoms. The aromatic substituents may themselves be optionally substituted. As used herein, when referring to a substituent as being optionally substituted, the substituent is unsubstituted or substituted by one or more substituents, unless otherwise specified. May be. Examples of suitable substituents are halogen atoms; alkyl groups; alkoxy groups; haloalkyl groups; haloalkoxy groups; acyl groups; acyloxy groups; amino groups, preferably alkylamino or dialkylamino groups; hydroxy groups; nitrile groups; And aromatic hydrocarbyl groups.

The fatty acid hydrocarbyl group is preferably an alkyl group, for example a C _1-4 alkyl group; or a cycloalkyl group, for example a C _3-6 cycloalkyl group. The aromatic hydrocarbyl group is preferably a phenyl group. The halogen atom in the halogen atom itself or a haloalkyl group in the form of a halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom. The acyl group in the acyl group, the acyloxy group or the acylamino group is preferably a C _2-5 alkanoyl group such as an acetyl group.

Examples of aromatic substituents containing an imino nitrogen atom are pyridyl, pyrazinyl, quinolyl, isoquinolyl, pyrimidinyl, pyridazinyl, cinnolinyl, triazinyl, quinoxalinyl and quinazolinyl. Preferred substituents are pyridyl and pyrimidyl. The imino group in the aromatic substituent containing an imino nitrogen atom is preferably attached to the phosphorus atom through only one bridging carbon atom. For example, if the aromatic substituent is a pyridyl group, it is preferably attached through a carbon atom to the 2-position of the pyridyl group. Thus, examples of preferred aromatic substituents containing an imino nitrogen atom are 2-pyridyl; 2-pyrazinyl; 2-quinolyl; 1-isoquinolyl; 3-isoquinolyl; 2-pyrimidinyl; 3-pyridazinyl;
Cinnolinyl; 2-triazinyl; 2-quinoxalinyl; and 2-quinazolinyl. 2-pyridyl, 2
-Pyrimidyl and 2-triazinyl are particularly preferred.

When the phosphine contains one phosphorus atom, it is advantageously of the general formula

Embedded image Wherein R ¹ represents an aromatic substituent containing an imino nitrogen atom, and R ² and R ³ are
The same or different and represents the group R ¹ or an optionally substituted aliphatic or aromatic hydrocarbyl group.

Particularly preferred phosphines are bisphenyl- (2-pyridyl) phosphine, bis (2-pyridyl)
Phenylphosphine, tris (2-pyridyl) phosphine, diphenyl (6-methoxy-2-pyridyl) phosphine, bis (6-ethoxy-2-pyridyl) phenylphosphine, bis (6-chloro-2-pyridyl) phenylphosphine, bis (6-bromo-2-pyridyl) phenylphosphine, tris (6-methyl-2-pyridyl) phosphine, bis (6-methyl-2-pyridyl) phenylphosphine, bisphenyl (6-methyl-2-pyridyl) phosphine, Bis (3-methyl-2-pyridyl) phenylphosphine, bisphenyl (4,6-dimethyl-
2-pyridyl) phosphine, di (n-butyl) -2-pyridylphosphine, dimethyl-2-pyridylphosphine, methylphenyl-2-pyridylphosphine, n-
Butyl tert-butyl 2-pyridylphosphine, n-butyl (4-methoxyphenyl) (2-pyridyl) phosphine, and methyldi (2-pyridyl) phosphine.

When the phosphine contains two phosphorus atoms, it is advantageously of the general formula

Embedded image It can be represented by, wherein at least one of R ^4, R ^5, R ⁶ and R ⁷ represents an aromatic substituent containing an imino nitrogen atom, R ^4, R ^5, R ⁶ and R ⁷ The rest of independently represent an optionally substituted hydrocarbyl or heterocyclic group, and X is 1 in the bridge
Represents a divalent bridging group containing from 10 to 10 carbon atoms.

The bridging group represented by X is preferably
It is a hydrocarbon residue, ether residue or thioether residue. For example, a crosslinking group

Embedded image Can be an alkylene chain optionally interrupted by one or more oxygen and / or sulfur atoms.

It is also

Embedded image May be a silane residue. The bridging group preferably contains 2 to 8 atoms, more preferably 3 to 5 atoms in the bridge. For example, when the bridging group is a propane residue, the bridge contains three atoms. Particularly high reaction rates were obtained when using organic diphosphines of the general formula (II) in which X represents a dialkyl ether residue. Therefore, it is preferable to use such a compound in the method of the present invention.

The remainder of R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably an optionally substituted alkyl group or an optionally substituted phenyl group. Most preferably,
They are an optionally substituted phenyl group. Examples of organic diphosphines that can be used in the method of the present invention are bis [(2-pyridyl) phenylphosphino] methane,
1,2-bis [(2-pyridyl) phenylphosphino]
Ethane, 1,3-bis [(2-pyridyl) phenylphosphino] propane, 1,5-bis [(2-pyridyl) phenylphosphino] -3-oxapentane, 1,8-bis [(2-pyridyl ) Phenylphosphino] -3,6-
Dioxaoctane, 1,3-bis [(2-pyridyl) butylphosphino] propane, and 1,3-bis [di-
(2-pyridyl) phosphino] propane.

[0021] The catalyst system used in the process of the present invention further comprises a protic acid. The role of the protonic acid is to provide a source of protons. Thus, the protonic acid may be generated in situ. Preferably, the protic acid is selected from acids having a non-coordinating anion. Examples of such acids are sulfuric acid; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, optionally substituted hydrocarbylsulfonic acids such as naphthalenesulfonic acid; alkylsulfonic acids such as methanesulfonic acid or Tert-butylsulfonic acid, or 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid or fluorosulfonic acid; phosphonic acids, such as orthophosphonic acid, pyrophosphonic acid or benzenephosphonic acid; carboxylic acids, such as chloroacetic acid , Dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid or terephthalic acid; or perhalic acids such as perchloric acid. The protic acid may also be an acidic ion exchange resin.

The catalyst system used in the process according to the invention can be homogeneous or heterogeneous. Preferably it is homogeneous. The ratio of moles of phosphine per gram atom of Group VIII metal is not critical. Preferably the ratio is 1 to 1000, more preferably 2 to 500, especially 1
It is in the range of 0 to 100. The ratio of moles of phosphine per mole of protic acid is not critical. The role of the protonic acid is to provide a source of protons. Therefore,
Protic acids may be generated in situ. Preferably it is in the range 0.1 to 50, more preferably 0.5 to 5. Examples of tertiary amines are optionally substituted aromatic heterocyclic tertiary amines such as pyridine, quinoline, isoquinoline, pyrimidine, pyrazine, triazole, triazine, pyridazine, purine, thiazole, benzimidazole, oxazole, pyrazole And an isothiazole; an aliphatic tertiary amine, for example, a dialkylamine such as dimethylamine or diethylamine; and an optionally substituted tertiary aniline, for example, N, N
-N, N-dialkylanilines such as dimethylaniline.

Preferably, the tertiary amine is pyridine or N, N-dialkylaniline. Preferred examples of pyridine are pyridine, alkyl-substituted pyridines such as 2,6
-Dimethylpyridine and polyvinylpyridine.
The number of equivalents of tertiary amine present per mole of proton is
Preferably it is at least 0.5, more preferably at least 1, even more preferably at least 2, especially at least 5. Depending on the particular carbonylation process in which the catalyst system is to be used, the tertiary amine is preferably present in a catalytic amount or in a solvent amount. When the tertiary amine is present in a catalytic amount, the number of equivalents of tertiary amine per mole of proton is
Preferably 0.1 to 200, more preferably 0.5
From 100 to 100, especially from 1 to 50.

When the tertiary amine is present in a solvent amount, the number of equivalents of tertiary amine per mole of proton is preferably 1
To 2500, more preferably 1.5 to 150
0, in particular in the range from 10 to 1000. To avoid ambiguity, the tertiary amine cannot be a phosphine, for example, a phosphine having an aromatic substituent containing an imino nitrogen atom.

Our co-pending UK Patent Application No. 9
0024911.0, a carbonylation catalyst system comprising: a) a Group VIII metal source; b) a phosphine source having an aromatic substituent containing an imino nitrogen atom; c) a proton source; and d) an alkylsulfonic acid anion source. And methods of using such catalyst compositions in the carbonylation of unsaturated compounds are disclosed and claimed.

Our co-pending UK Patent Application No. 9
No. 0025081 discloses: a) a source of a Group VIII metal; and b) a general formula

Embedded image Wherein R ¹ , R ² and R ³ are independently an optionally substituted aryl group and a general formula

Embedded image

Wherein A, X, Y and Z are each independently selected from a nitrogen atom, a CH group and a group represented by the formula CR, wherein R is a hydroxyl group, an amino group, an amide group. Represents a cyano group, an acyl group, an acyloxy group, a halogen atom, an optionally substituted hydrocarbyl group or an optionally substituted hydrocarbyloxy group, which is also at least one of R ¹ , R ² and R ³ Provided that one represents a group of formula (III), two adjacent CR groups are groups capable of forming a ring, and at least one of A and Z represents a group of formula CR )
Or a catalyst system comprising an acid addition salt thereof; and the use of such a catalyst system in the carbonylation reaction of an olefinic or acetylenically unsaturated compound is disclosed and claimed. Have been.

Our co-pending UK Patent Application No. 9
In 002509.9, a) a Group VIII metal compound; and b) a compound of the formula

Embedded image Wherein R ¹ represents an aliphatic hydrocarbyl group and R ² is a member of a larger fused ring structure wherein at least one of the ring atoms is nitrogen and is optionally substituted. Represents an optionally substituted aromatic heterocyclic group having 5 or 6 ring atoms capable of forming a moiety, and R ³ independently has the meaning of R ² , or Or an acid addition salt thereof, and the use of this catalyst system in the carbonylation reaction of unsaturated compounds is disclosed and claimed.

As mentioned above, it has surprisingly been found that the compositions of the present invention exhibit excellent activity in the carbonylation of unsaturated hydrocarbons. Accordingly, the present invention further provides a process for using the catalyst system as defined above in the carbonylation of acetylenically or olefinically unsaturated hydrocarbons. According to another aspect, the present invention relates to an acetylenically unsaturated compound comprising reacting an acetylenically unsaturated compound or an olefinically unsaturated compound with carbon monoxide in the presence of a catalyst system as defined above, or It is intended to provide a method for carbonylation of an olefinically unsaturated compound.

The acetylenically or olefinically unsaturated compound is preferably an asymmetric acetylene or olefin, most preferably alpha acetylene or alpha olefin. The olefinically unsaturated compound is preferably 2 to 30, preferably 3 to 2 per molecule.
A substituted or unsubstituted alkene or cycloalkene having 0 carbon atoms.
The acetylenically unsaturated compound is preferably a substituted or unsubstituted alkyne having 2 to 20, especially 3 to 10, carbon atoms per molecule. Acetylene or olefinically unsaturated compounds are
One or more acetylene or olefinic bonds, for example one, two or three acetylene or olefinic bonds, provided that two olefinic bonds are not adjacent and are not bonded to the same carbon atom Can be included.

The olefin or acetylene is, for example,
Halogen atom, cyano group, acyl group such as acetyl group, acyloxy group such as acetoxy group, amino group such as dialkylamino, alkoxy group such as methoxy, haloalkyl group such as trifluoromethyl, trifluoromethoxy Such as a haloalkoxy group, an amide group such as acetamido, or a hydroxy group. Some of these groups can participate in the reaction according to the exact reaction conditions.
For example, lactones can be obtained by carbonylating certain acetylenically unsaturated alcohols, such as 3-butyn-1-ol, 4-pentyn-1-ol or 3-pentyn-1-ol. In this way, 3-butyn-1-ol can be converted to α-methylene-δ-butyrolactone. Examples of alkynes are ethyne, propyne, phenylacetylene, 1-butyne, 2-
Butyne, 1-pentyne, 1-hexyne, 1-heptin,
1-octin, 2-octin, 4-octyne, 1,7-
Octadiyne, 5-methyl-3-heptin, 4-propyl-2-pentyne, 1-nonine, benzylethyne and cyclohexylethyne. Examples of alkenes are Ethene,
Propene, phenylethene, 1-butene, 2-butene,
1-pentene, 1-hexene, 1-heptene, 1-octene, 2-octene, 4-octene, cyclohexene and norbornadiene.

The acetylenically unsaturated compound or olefinically unsaturated compound is acetylene, as in, for example, 3-methyl-but-3-en-2-yne, and may also be an olefin. The catalyst system of the present invention has been found to be highly selective for acetylene groups in the presence of olefin groups. The unsaturated compounds may be carbonylated alone or in the presence of other reactants, for example, nucleophilic compounds having hydrogen or a removable hydrogen atom. Examples of nucleophilic compounds having a removable hydrogen atom are hydroxyl-containing compounds. The hydroxyl-containing compound is preferably an alcohol, water, carboxylic acid or silanol. The ability of the catalyst system of the present invention to carbonylate silanols is particularly surprising.

The alcohol used can be aliphatic, cycloaliphatic or aromatic and can have one or more substituents. The alcohol preferably contains up to 20 carbon atoms per molecule. It can be, for example, an alkanol, a cycloalkanol or a phenol. One or more hydroxyl groups may be present, in which case some products may be formed, depending on the molar ratio of the reactants used. Examples of alkanols are methanol, ethanol,
1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-methylpropan-1-ol, and 2-methylpropan-2-ol. Examples of phenols include phenol, alkylphenols, catechol, and 2,2-bis (4-hydroxyphenyl) propane.

Other classes of alcohols include polyhydric alcohols, especially lower sugars, such as glucose, fructose, mannose, galactose, saccharose, aldoxose.
e), aldpentose, altrose, allose, talose, growth, idose, ribose, arabonose, xylose, lyxose, erythrose or threose, cellulose, benzyl alcohol, 2,2-bis (hydroxymethyl) -1-butanol , Stearyl alcohol, cyclohexanol, ethylene glycol, 1,2-propanediol,
1,4-butanediol, polyethylene glycol, glycerol and 1,6-hexanediol. It has been discovered that an interesting reaction occurs when olefins are carbonylated with alkanols and formaldehyde in the presence of the catalyst system of the present invention. Without wishing to be bound by any theory, it is believed that the alcohol and formaldehyde react with each other to form hemiacetal. The hemiacetal, a hydroxyl group containing compound, then reacts with the olefin to form an alkyloxymethyl alkanoate. For example, ethene, carbon monoxide, formaldehyde and methanol can react with each other to produce methoxymethyl propionate.

The process of the present invention can be carried out using various types of carboxylic acids. For example, the carboxylic acid may be aliphatic, cycloaliphatic or aromatic, such as those named in relation to acetylenically unsaturated compounds and olefinically unsaturated compounds, and may contain one or more substituted May have groups. The carboxylic acids preferably used in the process according to the invention include carboxylic acids containing up to 20 carbon atoms. One or more carboxylic acid groups may be present, and thus various products can be obtained at will, depending on the molar ratio of the reactants used. The carboxylic acid can be, for example, an alkane carboxylic acid or an alkene carboxylic acid. Examples of carboxylic acids are formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, pivalic acid, n-valeric acid, n-caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, Benzoic acid, o-phthalic acid, m-
Phthalic acid, terephthalic acid and toluic acid. Examples of alkene carboxylic acids are acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid.

The silanol is preferably a trialkylsilanol, more preferably a tri (C _1-6 ) alkylsilanol, for example triethylsilanol. It will be appreciated that the unsaturated hydrocarbon and the hydroxyl group containing compound may be the same compound. When reacting an acetylenically unsaturated compound with water and carbon monoxide,
An α, β-unsaturated carboxylic acid is formed. When an alcohol is used instead of water, an α, β-unsaturated carboxylic acid ester is formed. When a carboxylic acid is used instead of water, an α, β-unsaturated anhydride is formed. α, β
The unsaturated products are, according to the reaction conditions used,
It can undergo further reactions.

When reacting olefinically unsaturated compounds with carbon monoxide and water, carboxylic acids are formed.
If an alcohol is used instead of water, a carboxylic acid ester will be formed; for example, the reaction of ethene, carbon monoxide and water will produce methyl propionate, and an acid anhydride if a carboxylic acid is used instead of water. A product is formed; for example, the reaction of ethene, carbon monoxide and propionic acid produces propionic anhydride. When silanols are used instead of water, silyl esters are obtained; for example, the reaction of ethene, carbon monoxide and triethylsilanol gives triethylsilyl propionate. The surprising property of the catalyst system of the present invention is that an unsaturated compound is selected by an acid-sensitive hydroxy compound such as a tertiary alkanol such as 2-methyl-propan-2-ol (tertiary butanol) and a silanol such as triethylsilanol. Is the ability to carbonylate it. Thus, according to a preferred aspect, the present invention relates to an acetylenically unsaturated compound in which an acetylenically unsaturated compound or an olefinically unsaturated compound is reacted with carbon monoxide and a tertiary alkanol or silanol in the presence of a catalyst system as defined above. It provides a method for carbonylation of unsaturated compounds or olefinically unsaturated compounds.

It has also been discovered that the catalyst system of the present invention is surprisingly good at the carbonylation of acetylenically unsaturated compounds in the presence of allene. Thus, according to a preferred aspect, the present invention provides a process for the carbonylation of acetylenically unsaturated compounds, wherein the acetylenically unsaturated compounds are reacted with carbon monoxide in the presence of allene and a catalyst system as defined above. Is what you do. Preferably, the arene is present in an amount of 0,1 based on the weight of the acetylenically unsaturated compound.
It is present in an amount of 3 to 10% by weight. When allene is present, the tertiary amine is preferably used in a catalytic amount.

The use of a separate solvent in the process of the invention is not essential. However, in some cases, it may be desirable to use a separate solvent. For that purpose, any inert solvent can be used. The solvent is, for example, a sulfoxide and a sulfone, such as dimethyl sulfoxide, diisopropyl sulfone or tetrahydrothiophene-2,2-dioxide (also called sulfolane), 2-methylsulfolane, 3-methylsulfolane, 2-methyl-4-butylsulfolane; Aromatic hydrocarbons such as benzene, toluene, xylene; esters such as methyl acetate and butyrolactone; ketones such as acetone or methyl isobutyl ketone; anisole; 2,5,8-trioxanonane (also called diglyme); diphenyl ether and diisopropyl It can consist of an ether, such as an ether, and an amide, such as dimethylacetamide or N-methylpyrrolidone. The process according to the invention is advantageously carried out between 10 ° C. and 2
It is carried out at a temperature of 00C, in particular in the range of 20C to 130C. The process according to the invention is preferably carried out at a pressure of 1 to 100 bar. Pressures higher than 100 bar can be used, but are generally not economically attractive because of the special equipment required.

The molar ratio of the hydroxyl group-containing compound to the unsaturated hydrocarbon can vary over a wide range and generally ranges from 0.
It is in the range of 01: 1 to 100: 1. The carbon monoxide required for the process according to the invention can be used in virtually pure form or diluted with an inert gas, for example nitrogen. The presence of more than a small amount of hydrogen in the gas stream is undesirable because hydrogenation of unsaturated hydrocarbons can occur under the reaction conditions. Generally, it is preferred that the amount of hydrogen in the supplied gas stream be less than 5% by volume. The catalyst system used in the process according to the invention consists of a liquid phase. These catalyst systems may be prepared in any convenient way. Thus, the catalyst system can be prepared by combining the separate Group VIII metal compound, phosphine (I), protic acid and tertiary amine in the liquid phase. Alternatively, they can be prepared in the liquid phase by combining the Group VIII metal compound and an acid addition salt of phosphine and a tertiary amine. Alternatively, they can be prepared in the liquid phase from a Group VIII metal compound which is a complex of a Group VIII metal and a phosphine, a protonic acid and a tertiary amine. Alternatively, they can be prepared in the liquid phase by combining a Group VIII metal compound, a phosphine and an acid addition salt of a tertiary amine.

The liquid phase may conveniently be formed by one or more reactants, including the catalyst system to be used. Alternatively, it may be formed by a solvent. It can also be formed by one component of the catalyst system, for example, a tertiary amine. Phosphines having an aromatic substituent containing an imino nitrogen atom are known in the art. They are conveniently prepared by reacting a phosphorus halide or an alkali metal phosphide with a suitable alkali metal or halide derivative of an aromatic compound containing an imino nitrogen atom.

The organic diphosphine having at least one aromatic substituent containing an imino nitrogen atom can be produced, for example, according to the method described in European Patent Application Publication No. EP-A2-03050512. Thus, for example, the organic diphosphine can be prepared by reacting a suitable alkali metal phosphide with a suitable dihalo compound.
The present invention will now be described by the following examples.

[0043]

EXAMPLES Preparation Example 1 Preparation of diphenyl- (6-methyl-2-pyridyl) -phosphine All operations were performed in an inert atmosphere (nitrogen or argon). The solvent was dried and distilled prior to use. 1.6 M hexane solution of n-butyllithium 36
ml was added to 40 ml of diethyl ether and the mixture was cooled to -40 ° C. Add 1 to the stirred mixture.
A solution of 0 g of 2-bromo-6-methylpyridine in 15 ml of diethyl ether was added over 20 minutes; the temperature was kept at -40 DEG C. during this addition. After the addition, the temperature is
The temperature was raised to 5 ° C., kept at that temperature for 5 minutes, and then lowered again to −40 ° C. A solution of 12.8 g of chlorodiphenylphosphine in 15 ml of diethyl ether was added to the stirred mixture over 15 minutes. After the addition, the mixture was warmed to room temperature, the solvent was removed in vacuo, and 50 ml of water and 50 ml of dichloromethane were added. After vigorous stirring for 5 minutes, the dichloromethane layer was separated. The aqueous layer was extracted twice with 50 ml portions of dichloromethane, the organic fractions were combined and the solvent was removed in vacuo. The residue was crystallized from toluene / hexane to give 12 g (75 g) of off-white crystals.
%) Of diphenyl- (6-methyl-2-pyridyl) -phosphine. The product is ³¹ P NMR: δp
= -5.6 ppm.

Preparation 2 Preparation of diphenyl- (3-methyl-2-pyridyl) -phosphine This compound was prepared in a manner analogous to that described in Preparation 1, but instead of 2-bromo-6-methylpyridine. 10.
0 g of 2-bromo-3-methylpyridine was used. It was characterized by @ ³¹ P NMR: .delta.p = -8.1 ppm.

Preparation 3 Preparation of phenyl-bis (6-methyl-2-pyridyl) -phosphine This compound was prepared in the same manner as described in Preparation 1, but instead of chlorodiphenylphosphine, 5.2 g of chlorodiphenylphosphine were used. Phenyldichlorophosphine was used. It is ³¹ P
NMR: characterized by δp = -5.1 ppm.

Preparation 4 Preparation of tris (6-methyl-2-pyridyl) -phosphine This compound was prepared in the same manner as described in Preparation 1, but instead of chlorodiphenylphosphine 2.7 g of trichloride. Phosphorus was used. It is ³¹ P NMR: δp = −
Characterized by 3.8 ppm.

Preparation 5 Preparation of diphenyl- (4,6-dimethyl-2-pyridyl) -phosphine This compound was prepared in the same manner as described in Preparation 1, but with 2-bromo-6-methylpyridine. Instead, 10.
8 g of 2-bromo-4,6-dimethylpyridine were used. It was characterized by ³¹ P NMR: δp = -5.6 ppm.

Preparation 6 Preparation of diphenyl- (6-methoxy-2-pyridyl) -phosphine 2.7 g in 100 ml of liquid ammonia at -80 ° C.
Of sodium and then 15.2 g of triphenylphosphine was added in six portions with stirring.
The solution was gradually warmed to −40 ° C., held at that temperature for 30 minutes, and then cooled again to −80 ° C. Then, 3.1 g of ammonium chloride was added to the stirred solution and 10.9 g of 2-bromo-6-methoxypyridine was added in three portions. The cooling bath was removed and the ammonia was evaporated. The residue was worked up with water / dichloromethane as described in Preparation Example 1. When crystallized from hexane, the slightly impure product ( ³¹ P NMR: δ
7 g (characterized by p = -4.4 ppm) were obtained, which was used as such in the examples hereinafter.

Preparation 7 Preparation of di (n-butyl) -2-pyridylphosphine 2.5 g of phenyl (2-pyridyl) ₂ P were added to 20 mol of tetrahydrofuran cooled to −80 ° C. and magnetically stirred. The dissolved solution was added over 10 minutes to 5.9 ml of a 1.6 M solution of n-butyllithium in hexane. After warming the resulting deep red solution to room temperature, the solution was analyzed by ³¹ P NMR and found to be (n-butyl) (2-pyridyl) PLi as the only phosphorus-containing compound (δp = -16.3 ppm). Phosphide. The solution was cooled to -40 ° C and a solution of 1.3 g of 1-bromobutane in 10 ml of tetrahydrofuran was added. The mixture was warmed again to room temperature, the solvent was removed in vacuo and 25 ml of diethyl ether and 10 ml of water were added. After stirring for 10 minutes, the organic layer was separated and the aqueous layer was extracted with 10 ml of ether. After the organic layers were combined, the solvent was removed in vacuo (66 Pa). Analysis of the resulting pale yellow liquid by ¹ H, ¹³ C and ³¹ P NMR indicated that the liquid was 2-
Phenylpyridine and (n-butyl) ₂ (2-pyridyl)
It was shown to consist of a 1: 1 (molar ratio) mixture with P (δp = -19.5 ppm).

Production Example 8 Preparation of dimethyl 2-pyridylphosphine and methylphenyl-2-pyridylphosphine Instead of the n-butyllithium solution, use 1.
The procedure of Preparation Example 7 was repeated except that a 6M solution of diethyl ether was used and 1.3 g of iodomethane was used instead of brombutane. The reaction product is almost 7
(Methyl) ₂ (2-pyridyl) in a ratio of 0:30:60
P, methylphenyl 2-pyridylphosphine and 2
A mixture of -phenylpyridines from which (methyl) ₂ (2-pyridyl) P was isolated by distillation. The physical properties of the product were δp = -41.2 ppm (dimethyl-2-pyridylphosphine) and δp = -2
4.1 ppm (methylphenyl-2-pyridylphosphine).

Production Example 9 Production of n-butyl tert-butyl 2-pyridylphosphine The procedure of Production Example 7 was repeated except that 5.6 ml of a 1.7 M solution of t-butyllithium in pentane was used instead of the n-butyllithium solution. The method was repeated. The final product was identified as n-butyl t-butyl 2-pyridylphosphine by NMR analysis (δp = -7.4 ppm).

Production Example 10 Production of dimethyl 2-pyridylphosphine 1.91 g of methyl (2-pyridyl) ₂ P and slightly 0.1%.
The method of Preparation Example 8 was repeated except that 7 g of iodomethane was used. Working up as described in Preparation Example 1 yielded dimethyl 2-pyridylphosphine, which was further purified by distillation (65% yield) (δp =
-41.2 ppm).

Production Example 11 n-butyl (4-methoxyphenyl) (2-pyridyl)
Preparation of phosphine All operations were performed in an inert atmosphere (nitrogen or argon). The solvent was dried and distilled prior to use. 1.6 M hexane solution of n-butyllithium 18
ml was added to 30 ml of diethyl ether and the mixture was cooled to -40C. To the stirred mixture,
A solution of 4.6 g of 2-bromopyridine in 15 ml of diethyl ether was added over 20 minutes; the temperature was kept at -40 DEG C. during this addition. After the addition, the temperature was raised to -5 ° C, kept at that temperature for 5 minutes, and then again
The temperature was lowered to 40 ° C. The resulting solution is
7.6 g of 4-methoxyphenyl-bis (2-pyridyl) -phosphine dissolved in ml of THF was added to a cooled (−40 ° C.) solution. The mixture was warmed to room temperature. After stirring for 10 minutes, the solvent was removed in vacuo.
Water (25 ml) and dichloromethane (25 ml) were added. After vigorous stirring for 5 minutes, the dichloromethane layer was separated. The aqueous layer was extracted twice with 25 ml portions of dichloromethane, the organic fractions were combined and the solvent was removed in vacuo. The residue was distilled, yielding 4.7 g (60%) of (n-butyl) (4-methoxyphenyl) (2-pyridyl) phosphine in the form of a yellowish liquid. This product is ³¹ P
NMR: characterized by δp = -14.9 ppm.

In this experiment, n-butyl lithium was reacted with 2-bromopyridine to form n-butyl bromide and 2
-It seems to give a mixture with lithium pyridyl. The 2-pyridyllithium then reacts with 4-methoxy-bis (2-pyridyl) phosphine to form 4-methoxyphenyl (2-pyridyl) lithium phosphide (and 2,2 ').
-Bipyridine). The lithium phosphide then reacts with n-butyl bromide to give (n-butyl) (4-methoxyphenyl) (2-pyridyl) phosphine.

Preparation Example 12 Preparation of methyl di (2-pyridyl) phosphine All operations were performed in an inert atmosphere (nitrogen or argon). The solvent was dried and distilled prior to use. 1.6 M hexane solution of n-butyllithium 36
ml was added to 40 ml of diethyl ether and the mixture was cooled to -40 ° C. To the stirred mixture,
A solution of 9.2 g of 2-bromopyridine in 15 ml of diethyl ether was added over 20 minutes; the temperature was kept at -40 DEG C. during this addition. After the addition, the temperature is -5 ° C.
And kept at that temperature for 5 minutes, then the temperature was lowered again to -40 ° C. A solution of 3.4 g of methyldiglycolphosphine in 15 ml of diethyl ether was added to the stirred mixture. After the addition, the mixture is warmed to room temperature, the solvent is removed in vacuo and
ml of water and 50 ml of dichloromethane were added. After vigorous stirring for 5 minutes, the dichloromethane layer was separated. The aqueous layer was extracted twice with 50 ml portions of dichloromethane, the organic fractions were combined and the solvent was removed in vacuo. The residue was distilled, yielding 4.0 g (68%) of methyl-bis (2-pyridyl) phosphine in the form of a yellowish liquid. This product was characterized by ³¹ P NMR: δp = -20.5 ppm.

EXAMPLE 1 0.1 mmol of palladium (II) acetate, 5 mmol of bisphenyl (2-pyridyl) phosphine, 4 mmol of paratoluenesulfonic acid, 50 ml of pyridine (620 mmol) were placed in a magnetically stirred 250 ml stainless steel autoclave. ) And 10 ml (65 mmol) of triethylsilanol. After the air was expelled from the autoclave, carbon monoxide (30 bar) and ethylene (20 bar) were added. Thereafter, the autoclave was sealed and heated to a temperature of 110 ° C. After reacting for 4.5 hours, a sample of the contents of the autoclave was taken out and analyzed by gas-liquid chromatography. Triethylsilyl propionate was formed with a selectivity of 60% (based on silanol). Di-triethylsilyl ether was also formed with a selectivity of about 40% (based on silanol). The average conversion rate was calculated to be 200 moles ethene / Pd gram atom / hour.

Comparative Example A The procedure was performed except that triphenylphosphine was used instead of bisphenyl (2-pyridyl) phosphine and a sample of the contents of the autoclave was taken after 5 hours instead of 4.5 hours. The method of Example 1 was repeated. Only trace amounts of triethylsilyl propionate were detected.

Comparative Example B The procedure of Comparative Example A was repeated, except that 50 ml of methyl propionate was used instead of 50 ml of pyridine and heated to 80 ° C. instead of 110 ° C. Di (triethylsilyl) ether was formed with a selectivity of more than 90%. Only trace amounts of propion triethylsilyl were detected.

Example 2 0.1 mmol of palladium (II) acetate, 5 mmol of bisphenyl (2-pyridyl) phosphine, 4 mmol of paratoluenesulfonic acid, 40 ml of pyridine (500 mmol) were placed in a magnetically stirred 250 ml stainless steel autoclave. ), 20 ml of methanol and 5 g of paraformaldehyde. The air was then expelled from the autoclave, followed by carbon monoxide (30 bar) and ethene (2 bar).
0 bar). Thereafter, the autoclave was sealed and heated to a temperature of 110 ° C. After reacting for 5 hours, a sample of the contents of the autoclave was taken out and analyzed by gas-liquid chromatography. Two products, namely,
Methoxymethyl propionate produced at a selectivity of 10% and methyl propionate produced at a selectivity of 90% were confirmed. Average reaction rate is 200 mol / P of ethene
It was calculated to be d-gram atoms / hour.

Comparative Example C The procedure of Example 2 was repeated using triphenylphosphine instead of bisphenyl (2-pyridyl) phosphine. Only traces of carbonylation products were observed.

Comparative Example D The procedure of Example 2 was repeated, but using 50 ml of methanol instead of 20 ml of methanol without using pyridine. After a reaction time of 2 hours, a sample of the contents of the autoclave was removed. Only traces of methoxymethyl propionate were observed. It was found that methyl propionate was formed with a selectivity exceeding 95%. The average reaction rate was calculated to be 1000 mol of ethene / Pd gram atom / hour.

Example 3 The procedure of Example 2 was repeated, but using 40 ml (350 mmol) of 2,6-dimethylpyridine instead of 40 ml of pyridine, heating to 125 ° C. instead of 110 ° C., and A sample of the contents of the autoclave was analyzed after 4.5 hours instead of 5 hours. It was found that methoxymethyl propionate was formed with a selectivity of 35% and methyl propionate was formed with a selectivity of 60%. The average reaction rate was calculated to be 150 mol of ethene / Pd gram atom / hour.

Example 4 The procedure of Example 2 was repeated, except that pyridine was used instead of pyridine.
Using ml (350 mmol) of 2,6-dimethylpyridine, using 10 ml of methanol instead of 20 ml of methanol and heating to 125 ° C instead of 110 ° C. It was found that methoxymethyl propionate was formed with a selectivity of 60% and methyl propionate was formed with a selectivity of 30%. The average reaction rate was calculated to be 100 moles ethene / Pd gram atom / hour.

EXAMPLE 5 0.1 mmol of palladium (II) acetate, 2 mmol of bisphenyl (2-pyridyl) phosphine, 10 mmol of paratoluenesulfonic acid, 40 ml of pyridine (500 mmol) were placed in a magnetically stirred 250 ml stainless steel autoclave. ) And 10 ml of methanol. After evacuation of the autoclave, 20 bar of ethene and 3 bar
0 bar of carbon monoxide was added. Thereafter, the autoclave was sealed and heated to a temperature of 110 ° C. After reacting for 5 hours, a sample of the contents of the autoclave was taken out and analyzed by gas-liquid chromatography. It was found that methyl propionate was formed. Average reaction rate is ethene 3
It was calculated to be 00 mol / Pd gram atom / hour. No methyltriphenylphosphonium paratoluenesulfonate was detected, indicating that the catalyst remained stable during the course of the reaction.

Comparative Example E The procedure of Example 5 was repeated, except that bisphenyl (2-pyridyl) phosphine was replaced by triphenylphosphine. Methyl propionate was detected, but the average reaction rate was calculated to be 10 mol ethene / Pd gram atom / hour.

COMPARATIVE EXAMPLE F Using tris (p-chlorophenyl) phosphine instead of bisphenyl (2-pyridyl) phosphine, using 4 mmol of paratoluenesulfonic acid, heating to 130 ° C. and after 4 hours The procedure of Example 5 was repeated except that the sample was removed from the autoclave. Methyl propionate was detected. Average reaction rate is ethene 1
It was calculated to be less than 0 mol / Pd gram atom / hour.

Example 6 The procedure of Example 5 was repeated, but using 40 ml (320 mmol) of N, N-dimethylaniline instead of 40 ml of pyridine, heating to 100 ° C. instead of 110 ° C., and The sample was removed from the autoclave after 1.5 hours instead of 5 hours. Methyl propionate was formed.
The average reaction rate was calculated to be 700 moles of ethene / Pd gram atom / hour.

Example 7 The procedure of Example 5 was repeated, but using 20 ml (270 mmol) of propionic acid instead of 20 ml of methanol and heating to 90 ° C instead of 110 ° C. Propionic anhydride formed. The average reaction rate was calculated to be 250 moles ethene / Pd gram atom / hour.

Example 8 The procedure of Example 5 was repeated, but using 5 mmol of bisphenyl (2-pyridyl) phosphine, 4 mmol of paratoluenesulfonic acid, 30 ml of methanol and heating for 3 hours instead of 5 hours. . Methyl propionate was formed. The average conversion rate was calculated to be 800 mol ethene / Pd gram atom / hour.

Example 9 The procedure of Example 5 was repeated, but using 5 mmol of bisphenyl (2-pyridyl) phosphine, 4 mmol of trifluoromethanesulfonic acid, and after 3 hours a sample of the contents of the autoclave was removed. . Methyl propionate was formed. The average reaction rate is ethene 1000 mol / P
It was calculated to be d-gram atoms / hour.

Example 10 The procedure of Example 5 was repeated except that 5 mmol of bisphenyl (2-pyridyl) phosphine, 4 mmol of paratoluenesulfonic acid, 50 ml of methanol instead of 20 ml and 10 g of 40 ml of pyridine were used. (95 mmol)
Of poly-4-vinyl-pyridine (cross-linked) was used. The average reaction rate was calculated to be 400 moles of ethene / gram atom of Pd / hour.

Example 11 0.025 mmol of palladium (II) acetate, 1 mmol of bisphenyl (6-methyl-2-pyridyl) phosphine, 2-methyl-2-propylsulfone were placed in a magnetically stirred 300 ml stainless steel autoclave. 2 mmol of acid, 30 ml of methyl methacrylate as solvent, 30 ml of methanol and 10 mmol of dimethylaniline were successively charged. Then, after purging air from the autoclave, 30 ml of propyne containing 0.4% of allene was added.
Subsequently, carbon monoxide was added to a pressure of 60 bar. Thereafter, the autoclave was sealed and heated to a temperature of 60 ° C. After reacting at 60 ° C. for 0.1 hour, a sample of the contents of the autoclave was analyzed by gas-liquid chromatography. From the analytical results, the selectivity to methyl methacrylate was calculated to be 99.94% and the average conversion rate to be 90,000 moles of propyne / Pd gram atom / hour. Examples 12 to 18 and Comparative Example G The procedure of Example 11 was repeated using a different tertiary amine from Example 11 and using different amounts of allene in propyne. These results are summarized in Table 1. These results indicate that the inhibitory effect of allene on the catalyst can be neutralized by using a tertiary amine.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B01J 21/00-37/36

Claims (3)

(57) [Claims] 1. An acetylenically unsaturated compound or olefin comprising: a) a Group III metal source; b) a phosphine having an aromatic substituent containing an imino nitrogen atom; c) a proton source; and d) a tertiary amine. Catalyst system for carbonylation of unsaturated compounds. 2. The catalyst system according to claim 1, wherein the tertiary amine is pyridine or N, N-dialkylaniline. 3. An acetylenically unsaturated compound or an olefinically unsaturated compound comprising reacting an acetylenically unsaturated compound or an olefinically unsaturated compound in the presence of a catalyst system as defined in claim 1 or 2. Carbonylation method.